Anionic dispersion of a salt of a cationic dye and a selected arylsulfonate

ABSTRACT

An aqueous dispersion of (1) a water-insoluble salt of a cationic dye and a selected anion of an arylsulfonic acid with (2) an anionic dispersing agent selected from lignin sulfonate or a salt of a sulfonated naphthalene-formaldehyde condensate. The salts can be represented by the formulas D Ar&#39;&#39;SO3 and K ArSO3 where D is a cationic dye having a resonating or delocalized positive charge and Ar&#39;&#39; is an aryl group substituted with substituents such that the summation of the pKa increments for the substituents is equal to or less than -0.9; and K is a cationic dye having a localized positive charge and Ar is an aryl group substituted with substituents such that the summation of the pKa increments for the substituents is equal to or less than -0.6. The aqueous paste dispersions of the salts can be employed to dye acid-modified polyamide,polyester, or acrylic fibers, either alone or in a blend, by a number of dyeing techniques, including Thermosol, Pad Steam, Pad Roll or Exhaust Dyeing.

United States Patent 1 1 Clarke et al.

[4 1 Oct. 16, 1973 [22] Filed: Apr. 25, 1968 [21] Appl. No.: 724,238

[52] US. Cl. 8/41 A, 8/89, 8/173, 8/168, 8/21 D, 8/21 C, 8/17, 8/41 B, 8/41 C, 8/172 [51] Int. Cl D06p 3/18 [58] Field of Search 8/89, 1214, 172, 8/173, 21, 177, 178, 179; 106/22, 27, 308 N, 308 S [56] References Cited UNITED STATES PATENTS 1,613,228 1/1927 1102 et a1. 8/172 X 2,768,054 10/1956 Armento i 8/173 X 2,848,296 10/1958 Heller 8/173 2,922,690 l/1960 Mueller et a1. 8/21 3,288,551 11/1966 Roff r r 8/172 X 3,185,538 5/1965 Voltz et a1. 8/173 6/1967 B osshard 8/62 x 7/1967 Lewis Primary Examiner-D0nald Levy AttorneyGary A. Samuels [57 ABSTRACT An aqueous dispersion of l) a water-insoluble salt of a cationic dye and a selected anion of an arylsulfonic acid with (2) an anionic dispersing agent selected from l'ignin sulfonate or a salt of a sulfonated naphthalene-formaldehyde condensate.

The salts can be represented by the formulas D ArSO and K ArSO where D is a cationic dye having a resonating or delocalized positive charge and Ar is an aryl group substituted with substituents such that the summation of the pKa increments for the substituents is equal to or less than O.9; and K* is a cationic dye having a localized positive charge and Ar is an aryl group substituted with substituents such that the summation of the pKa increments for the substituents is equal to or less than 0.6.

The aqueous paste dispersions of the salts can be employed to dye acid-modified polyamide,polyester, or acrylic fibers, either alone or in a blend, by a number of dyeing techniques, including Thermosol, Pad Steam, Pad Roll or Exhaust Dyeing.

12 Claims, No Drawings ANIONIC DISPERSION OF A SALT OF A CATIONIC DYE AND A SELECTED ARYLSULFONATE BACKGROUND OF THE INVENTION 1. Field of the Invention This invention is directed to novel dyeing compositions useful in the dyeing and printing of acid-modified acrylic, polyamide, and polyester fibers.

2. Description of the Prior Art Acid-modified acrylic fibers, such as those described in U.S. Pat. Nos. 2,837,500 and 2,837,501, and acidmodified polyesters, such as those described in U.S. Pat. No. 3,018,272, have become widely used in textile applications and methods for continuously dyeing them have been sought. Early dyeing compositions employed to dye these fibers were conventional basic dyes in the form of their water-soluble salts. These early compositions, when used in the most common continuous dyeing methods, i.e., pad steam or Thermosol, exhibited low fixation, poor build-up, and low solubility limited shades obtainable to light-to-medium depths.

In addition, the concurrent growing use of fiber blends, e.g., a fiber blend of acid-modif1ed polyacrylonitrile or polyester and a cellulosic polymer or a natural fiber such as wool, prompted additional need for new dyeing compositions. To dye the different types of fibers of the blend in the same dye bath presented complex problems which made necessary a careful consideration of the time of addition of the different types of dyes needed to dye each of the different types of fibers present, and a careful consideration of the compatability of the different types of dyes. Frequently, an anionic dye used to dye cotton or wool was found to coprecipitate with the basic cationic dye used to dye the acid-modified synthetic polymer. For the same reason, the economical and effective anionic thickeners and anionic dispersants did not give good results when employed with the basic cationic dyes in dyeing acidmodified polymer blends. Limited success for obtaining compatibility of cationic dyes with anionic agents has been achieved for pad bath operations, but requires the presence of a non-ionic surfactant.

Partial alleviation of the compatibility problems associated with the use of cationic dyes with anionic thickeners or dispersants was effected by employing a dyeing or printing composition of the water-insoluble complex formed from a basic cationic dye and a heteropoly acid in admixture with a dispersant formed by the sodium salt of the condensation product of formaldehyde and Z-naphthalene sulfonic acid. Such compositions are described in Canadian Pat. Nos. 737,934, 737,960 and 775,458. However, these compositions, although improving the compatability properties are not entirely satisfactory because (1) they do not build up well on the fiber with increasing dye concentration, (2) not all dye on tone with respect to the parent cationic dye color because duplication of shade is difficult, and (3) they are not applicable to fibers by a continuous Thermosol procedure.

Thus, the objects of this invention are to provide dye compositions which give good build-up on fibers with increasing concentration which are stable over prolonged periods of time, give level dyeings while maintaining shade, and which are applicable by a continuous Thermosol process. In addition, other objects of this invention are to provide dye compositions which are compatible with other dye bath ingredients such as anionic dyes, acid dyes, anionic thickeners, pad liquors, etc.; which are applicable to high temperature, continuous application without pretreatment of the fiber substrate, which are applicable to fiber substrates by pad steam, pad roll, printing or exhaust dyeing techniques; which yield a negligible stain on cotton, nylon or unmodified polyesters; and which are stable over a wide pH range, e.g., 2 to l0.

These and other objects which will become apparent hereinafter are accomplished bythe compositions of this invention.

SUMMARY OF THE INVENTION The compositions of this invention comprise an aqueous dispersion of l. a water-insoluble salt of a cationic dye and a selected anion of an arylsulfonic acid, and

2. an anionic dispersing agent selected from lignin sulfonate or a salt of a sulfonated naphthaleneformaldehyde condensate.

The cationic dye component of the salt is selected from (a) cationic, basic dyes having a delocalized, or resonating, positive charge, and (b) cationic dyes having a localized, i.e., pendant, positive charge represented by the formula Ra ili z-v-iiiN-m i Tube 1 5E fi s aye 11656;?

Y is a connecting linkage selected from a covalent bond, alkylene of one to six carbon atoms,

MI and the like);-

Ar'SO in which Ar is a carbocyclic aromatic moiety containing 6 to 14 ring carbon atoms, with the provisos that Ar is devoid of water-solubilizing or ionogenic substituents, and that Ar is substituted with substituent groups such that the summation of the pKa increments for the substituents, as measured on benzoic acid derivatives in aqueous medium, is equal to or less than -0.9.

When the cationic dye is one having a localized, pendant positive charge, the arylsulfonic anion is represented by the formula Arso? wherein D represents a cationic, basic dye having a resonating or delocalized positive charge; Ar and Ar are as defined above; and K represents a cationic dye having a localized, pendant positive charge represented by the formula wherein Z, Y, R,, R R and R areas defined prev i ously.

DETAILED DESCRIPTION OF THE INVENTION A. THE SALT OF THE DELOCALIZED POSITIVE CHARGED DYE AND THE ANION Ar'SO? 1. The Cation 13 The cationic, i.e., basic, dyes with a delocalized, resonating, positive charge that are operable in the salt component of the compositions of this invention encompass a wide variety of dyes distinguished by the fact that their positive charge is not localized on a single atom, but rather is delocalized through resonance between various atoms of the dye structure. Resonance is a term describing a well-known phenomenon of chem istry. See, for example, Mechanism and Structure in Organic Chemistry, by E.S.Gould; Henry Holt and Co., New York, 1959, and The Chemistry of Synthetic Dyes, Vol. I, Chapter V, by K. Venkataraman, Academic Press, Inc., New York, 1952. According to the resonance theory, when a compound can have two or more structures that are equivalent or nearly so and that are interconvertible by the redistribution of electrons or ionized centers, the actual molecule does not conform to any one of the structures but exists as a resonance hybrid of them all. That is, all the canonical forms possible contribute to the true structure (the resonance hybrid). Thus the triarylmethane dye, Rosaniline, is a resonance hybrid composed of several major cononical' forms shown as follows:

4 HzN l atoms containing either an unshared pair of electrons ;or a pair of electrons available for delocalization as the fpi (1r) electrons which form multiple or aromatic bonds is covered by this definition.

The following dye structures are illustrative of the' icationic dyes having a delocalized positive charge efifective for use in the compositions of this invention:

@f-(Q i 0 CHgCH: C N);

This dye, where R is Cl, is described iiful'sTi siiivbf 3,021,344. 2. The formula I dye wherein R is H is described in US. Pat. No. 2,083,888.

TWyeTwFei-Ein R is i l {is desc i ibedih Usf l afi oi 2,155,459. 4. The dye of formula 3 where R is -OCH f This dyeis described in US. Pat. No. 3,l92,l95.

4S 6. Cl. 48,036

E OH:

CH: 11.0 i

GH=CH N N CH:

.HiNe CI? HaC This dye is disclosed in U.S. Pat. No. 2,164,793 and U.S. Pat. No. 2,734,901. 9. The dye of formula 8 wherein R is The dye is disclosed in U.S. Pat. Nos. 2,164,793 and 2,734,901. 10. The dye of formula 8 wherein R is Cal-I The dye is disclosed in the patents discussed under 8.

( :Hs):N m irmr \C/ gowns The corresponding methyl ester is C.I 45,175.

13. The dye of formula 8 wherein R is cmcmcN 14. The dye of formula 8 wherein R is The dye is disclosed in U.S. patents discussed in No.8.

mo cm fea The dye is disclosed in U.S. Pat. No. 3,068,056. 16. The dye of formula 15 wherein R is The dye is disclosed in U.S. Pat. No. 3,121,711.

1 L CH 2 R =H, Rz=H The dye is disclosed in U.S.Ser.No. 579,188, filed Sept. 14, 1966.

18. The dye of formula 17 wherein R is Cl and R 2|. The dye of formula 8 wherein R is The dye is disclosed in U.S. Pat. No. 2,077,063.

zHgON The dye is disclosed in U.S. Pat. No. 2,741,605.

24. The dye of formula 8 wherein R is 7 8 I I 32. H CH; @PHCHzCHzCNh. I 1 1$ \CC/ ll The dye is disclosed in Japanese Pat. No. 13,748/66 5 12mm i l O II-Ia 25. i 7 alls The dye is disclosed in US. Pat. No 3,0l4,Q4 l.

ea s w cmcmcN CH: 2 NN i A 8 H N=N HO: I 26. The dye of formula 8 wherein R is 5H N @OCHa) r C=CH-N= 27. The dye of formula 8 wherein R IS v CHiCHICN (EH: .N\ I

CHICHICI The dye is related to thedyes disclosed in 1.1.8. Pat.

28; CH; N$\ I I 30 35. (O) HO CN=NN(CH3)= N=N s cm O i The dye is disclosed in US. Pat. No. 2,893,816., The dye is disclosed in [1.3. Pat. No. 3,312,681.

36. I S 2 s 40 cmo i c-@-N=N-cH-ecm CN=N-R 0:4: /N

v N (BI? IE; I wherein R is The dye is disclosed in us. Pat. NO. 1,833,839.

CzH4Ok-C0Hs Q I s7, 7 11.0 CH; 30. The dye of formula 29 wherein R is I /CH:-CH2 CH=CH-R h Bi N CH. /CHCH:CN w are S @N CH: I 13H; v. 3* I f The dye is disclosed in us. Pat. NO. 2,077,063.

(BN\ 38. The dye of formula 37 wherein R. is

/CN=N I I CHz-CHn s 06H \N/ N/ Q \CH:.

The dye is disclosed if! US. Pat. No. 2,893,816.- CH;

I 39. The dye of formula 37 wherein R is one-H,

40. The dye of formula 37 wherein R is CHI-CH:

Thus representative basic dye classes which are suitable for reaction with arylsulfonic acids to form the water-insoluble (at room temperature) salts employed in the present invention include the following: diphenylmethanes (ketone imines) such as auramine; triarylmethane dyes such as C.l. Basic Green 1, C.l. 42,040, fuchsine (C.l. 42,500), resorcine violet (C.l. 43,520), victoria blue (C.l. 44,040), basic violet (C.l. 42,577)(Suppl.), rhoduline violet(C.1.44,520), the basic dyes of U.S. Pat. No. 3,021,344 (1962) to D.R.Baer; of U.S.Pat. No. 3,032,561 1962-)to J.Pikl; of U.S. Pat. No. 2,083,888 (1937) to Carl Winter et al.; xanthene dyes such as Pyronine G (C.l. 45,005), methylene red (C.l. 45,006), Rhodamine S (C.l. 45,050), saccharein (C.l. 45,070), Rhodamine G (C.l. 45,105), Rhodamine G (C.l. 45,150), Rhodamine6G (C.l. 45,160), Rhodamine 12GM (C.l. 45,310); acridines such as Acridine Orange NO (C.l. 46,005), Diamond Phosphine GG (C.l. 46,035), Rheonine AL (C.l.

46,075); methine dyes such as basic red C.l. 48,015, A

basic red C.l. 48,013, basic violet C.l. 48,020, basic orange C.l. 48,035, basic yellow.C.1. 48,055, basic red C.l. 48,070, basic yellow C.l. 48,060, basic yellow C.l. 48,065, basic dyes prepared from 2-methylene-1,3,3- trimethylindoline (Fischers Base) as disclosed in U.S. Pat. No. 2,734,901 and in Synthetic Dyes' by Venkataraman, Academic Press lnc., New York, 1952, vol. 11, page 1 174, basic methine dyes as described in U.S. Pat. Nos. 2,155,459 and 2,164,793, basic azatrimethinecyanine dyes such as those disclosed by .l. Voltz in "Angew. Chem." (English edition) pages 532-537, October 1962; thiazole dyes such as Thioflavine T (C.l. 49,005); indamine basic dyes suchas basic green C.l. 49,405; azine dyes such as Mauve (C.l. 50,245 Safr'anine T (C.l. 50,240 basic violet C.l. 50,055, basic blue C.l. 50,306, lnduline 68 Base (C.l. 50,400); oxazine dyes such as basic blue C.l. 51,004, Mendolas Blue C.l. 51 ,175, basic black C.l. 51,215; thiazine dyes such as Methylene Blue C.l. 52,015, basic green C.l. 52,020; and azo dyes having a delocalized positive charge such as the azo-safranine dyes described in U.S. Pat. No. 3,068,056 and U.S. Pat. No. 3,121,711, chrysoidine C.l. 11,270, basic brown C.l. 21,010, and basic dyes of British Pat. No. 896,681; u.s. Pat. Nos. 2,864,812, 2,864,813, 2,883,373, and 2,889,315; 2,906,747, and German Pat. No. 1,088,631.

The preceding list of dyes represents preferred classes of dyes and is not to be construed as being restrictive. The list is intended to exemplify the wide variety 2. The Anion ArSO? The cationic dyes discussed in Part A( 1) immediately above are most commonly taught in the patent literature as possessing adequate water solubility. Water solubility is achieved by preparing the dye as salts with anions usuallyselected fromthe following list: C19 Br 9 H80 9 11 F0 9 l/2SO,6, ZnCI Q CH SO l5 9 4 Q- aQ i ll 3 9 i C2H5'O SO3 C H SO 9 CH -C H SO 9 (ortho or para),

HCOO CH -COO C H -COO9 C,,H -COO 6 Cl2-COO C H CoO the lactate, oxalate, tartrate or citrate ion. When produced with these ions, the dyestuffs are sufficiently soluble in water to be applicable to polyacrylonitrile fibers from aqueous solution. I

1n the present invention, selected substituted carbocyclic arylsulfonates, Ar'S,O are employed in place of the water-solubilizing anions described above. These selected arylsulfonates provide tight salts with the cationic dye which are water-insoluble at room temperature, may be dispersed with selected anionic dispersing agents, are compatible (i.e.,do not co-precipitate by ion exchange) with aciddyes, anionic thickeners, and like ingredients of dye baths, and which fulfillthe objectives of this invention as stated previously. In particular, they may be applied by a continuous Thermosol technique to acid-modified polyacrylonitrile and polyesters. 1

The substituents permissible on the carbocyclic arylsulfonate may vary widely. It has been found that permissible substituents on the arylsulfonates are those whose combined effect increases the acidity of the corresponding benzoic acids to a certain degree. More specifically, it has been found that any substituents which increase the acidity of benzoic acids, in an aqueous medium-by at least 0.9 of a pKa unit, when added together, are useful substituents for the carbocyclic aromaticsulfonic acids used ascomplexing anions with thedelocalized charge cations in this invention. Thus, on pages 592-593 of the Determination of Organic HsC ApKa=-1.04 ApKa=-2.79

in addition, the following monosubstituted benzenesult'onic acids may be employed as complexing anions useful in attaining the objectives of this invention A pKa onitrobcn zenesulfonate 2.03 o-iodobenzenesulfonate l.34 o-bromobenzencsulfonate -l .35 o-chlorobcnzenesulfonate l.26 o-l'luorobenzcncsulfonate 0.93

The list for operable polysubstituted carbocyclic aromatic sulfonates becomes much larger since the effects appear to be additive, as previously illustrated with the two preferred compiexing agents. For example, the following complexing anions may be specifically mentioned as applicable:

ApKa 3-methylsulfonyl-5chlorobenzenesulfonate -0.93 3-trifluoromethyl-5-cyanobenzenesulfonate -l .01 2-ethyl4-methylsulfonylbenzenesulfonatc l .l l 2,4-, 2,5-dichlorobenzenesulfonate l .47, l.63 2-phci1oxy-S-chlorobenzenesulfonate l .04

Other polysubstituted benzenesulfonic acids, useful in this invention are also suggested by the data on pages 594-595 of the Braude reference. On these two pages, pKa values, are listed as compared to the reference, benzoic acid itself. Since a lower pKa than benzoic acid, 4.20, indicates a stronger acid than benzoic, a simple subtraction of the listed values from 4.20 gives the ApKa. Thus, based on pages 594-595, the following benzene-sulfonates are also applicable in this invention. Many of these pKa values are somewhat surprising based on the values given for the monosubstituted benzoic acids shown on page 592-593. These apparent anomalies are usually rationalized on the basis of steric effects, as well as their electrical, i.e., inductive and resonance effects.

ApKa 2,6dimethylbenzenesulfonate -0.99 2,4-dibromobenzenesulfonate -l .50 2,5-dinitrobenzenesulfonate -2.5 8 3,4-dinitrobenzenesulfonate l .38 2-nitrn-4,S-dimethoxybenzcnesulfonate l .71 2,3-dinitro-5,6-dimethoxybenzenesulfonate -2.84

Additional substituted compounds are effective in this invention. Several are listed below with reference to their Hammett sigma constants. The pKa limitation is not altered here since the Hammett sigma constants can be derived from the degree of dissociation, i.e., ionization or pKa of substituted benzoic acids in an aqueous medium. A convenient list of Hammett sigma constants is available on p.87 in Physical Organic Ghemistry," 2nd Edition, by .l. Hine, McGraw-Hill Book Co., lnc., 1962. Using Hammett sigma constants, the requirement is that sigma be equal to or greater than +0.9. This requirement is the equivalent of the requirement that the sum of the pKas be equal to or less than 0.9. Thus, the following compounds may be employed:

Hammett Sigma Value 3-cyano-4-acet0 benzenesull'onate H .06 S-carboethoxy-4-cyanobenzenesulfonate +l .03 3-acetamidoA-methylsulfon ylbenzenesulfonate +0.93 3,S-disulfonamidobenzenesulfonatc +0.92 3'acetoxy-4-sull'amylbenzenesulfonatc +0.96 B-methylsulfoxy-4-benzoylbenzenesulfonate +0.98 3-nitro-4-p-nitrophenylbenzenesulfonate +0.97 3-methylthio-4-nitrobenze nesulfonate +0.94 3-phen0xy-4-cyanobenzenesulfonate +0.91

Finally, several compounds are readily applicable as anions in this invention, for which ionization data is not conveniently found in the literature. Thus, in changing from benzene to naphthalene sulfonates, more than just the ionization constant must be considered to describe the effect on the solubilitiy of the cationic dye salts. For example, although the pKa values of benzoic acid and B-naphthoic acid are similar (3.20 and 3.16, respectively), the latter is 30 times less soluble. It is readily seen, however, since B-naphthoic aicd is more insoluble thann benzoic acid that the limitation that the pKa of the substituents be equal to or less than 0.9 applies equally to these latter compounds. Some such compounds include 5-, and B-acetamido-2-naphthalenesulfonate l-, and 2-anthraquinonesulfonate 2-chloro-3,S-dinitrobenzenesulfonate Z-chloro-S-nitrobenzenesulfonate 4-chloro-3-nitrobenzenesulfonate 8-cyano-l-naphthalenesulfonate 1-, and Z-naphthalenesulfonate 5-, and 8-nitr0-l-naphthalenesulfonate 5, and 8-nitro-2-naphthalenesulfonate 2,6-dimethyl-8-, and -3-naphthalenesulfonate and Acenaphthene-3-sulfonate lt has been found that dyes illustrated by formula 3 will form water-insoluble, dispersable salts with a weaker sulfonate than generally applicable, for example, m-nitrobenzenesulfonate; and that to obtain waterinsoluble crystalline precipitates, necessary for preparing good dispersions, with dyes represented by formulas 19 and 22, very strongly acidic sulfonates are more desirable, for example, 2,4-dinitrobenzenesulfonate. These conditions are preferred ones for use with the specified dyes.

B. THE SALT OF THE LOCALlZED, PENDANT POSITIVE CHARGE DYE AND THE ANION ArSO? l. The Cation K The cationic dyes having a pendant, localized positive charge which are useful in the salt with ArSO} have been previously defined as having the structure group thereby prevents any resonance interaction, i.e.,

delocalization, of the pi electrons of the chromophore with the positively charged center. Thus, since an insulating, alkylene group is present, this type of cationic dye is commonly described as a pendant basic dye.

The following structures are illustrative of the cationic, K dyes effective in the salt component of this invention:

13 14 Disclosed in US. Pat. No. 2,099,525 Disclosed in -P 42. 01 CH C 1 1 49. o 1 ON N=N-@ N\ e CH 9 CH ("1 I C,HN (C,H5) 1)1N N N- NHC;H4CN CH1 i Related to dyes disclosed in US. Pat. No. 2,972,508. Disclosed in Us Pat. 2,821,526

1 CgHs so. 0 9 ll, O;N@N=N-@N\ g (CHahN-CHz- N=N C7H(N(CH3): (I

Related to dyes disclosed in us. Pat. N0. 2,972,503 Disclosed in 6- A) Disclosed in us. Pat. N0. 2,821,526.

52. 0 (31115 .I q; ([5 Disclosed in US. Pat. No. 2,888,467. N:N

. CH 02H: 45. a

- C7H5 iL N/ s D1scl0sed 1n U.S. Pat. No. 2,821,526.

C H4N(CHa)a Disclosed in US. Pat. No. 2,972,508. Quaternary d es of us. 3,023,212 as 46. I 40 OH g E a I 6 O1 0/ -NH(CHz):N(CHa)2 NmCHmINwHm CH:

Related IO the dyes in us. Pat. NO. 2,183,652. Pref- Disclosed in US. P31. No. 3,023,212 and us. Pat. erab'y obtained the No. 2,834,793. Preferably obtained as the HCl salt.

. 4 O NH:

9 O NH-CHaCHzCHaN (CH3)! Disclosed in us Pat. No. 2,834,793 as the Hc1 salts.

Disclosed in US. Pat. No. 2,716,655.

The quaternary dyes off U.S. Pat. No. 2,701,802, preferably obtained as the HCl salt.

EB Y N H( 2)a C a):

Similar to the dyes of U.S. Pat. No. 2,153,012

Disclosed in U.S. Ser. No. 560,867, filed June 27,

QB z a 3):

Disclosed in us. Ser. No. 490,053, filed Sept. 24, 1965.

Disclosed in U.S Ser. No. 494,875, filed Oct. 11, 1965.

Cal-LN (CH Diselosed in Us. Pat. No. 3,020,272.

Disclosed in U.S. Ser. No. 494,875, filed Oct. H,

Disclosed in U.S. Pat. No. 3,074,926.

Disclosed in U.S. Ser. No. 494,875, filed Oct. 11,

73. CH3 CH3 N CH SOr -NN -N/ Disclosed in U.S. Pat. No. 3,033,847.

I I e CH om N N@ unmrm u 5 Disclosed in U.S. Pat. No. 3,079,377.

0 (cH=)-cm 110-- Disclosed in U.S. Pat. No. 2,965,631.

I G CHIN(CHI)I in U.S. Pat. No. 2,022,921, as

Dyes 79 and 80 are described in copending application of Clarke, filed Nov. 6, 1967, Ser. No. 680,994.

81- 82. Quaternary derivatives of the dyes described 83. Quaternary dyes of U.S. Pat. No. 2,099,525, as

84-87. Quaternary dyes, described in Pat. No.

88-89. The niono-cationic dyes of U.S. Pat. No.

OCH; OCH:

CH; 69/ zHaN-CzHaO corresponding quaternary derivatives as Cl OCH: HO -NH- 1 1 1 y ON- -N=N N=N 6 3 H:N(CH1): ('11 00111 C) 90-91. The non-metalized, quaternary derivatives of the dyes of U.S. Pat. No. 3,096,318, as

92-93. The non-meta11ized, quaternary derivatives of 100. The quaternary dyes 98. The dyes of French Pat. No 1,271,416, as

1 CH: I H O-CHaCHn-N-CI-Ia-C O N=N 1 1 I CH: CGHS I I 99. The dyes of French Pat. No. 1,295,862, as

0fU.S. pat. No. 2,701,801,

the dyes of U.S. Pat. No. 3,099,652, as as cur-cm s 0 NH: 0

0 \N-CHQCH:CH2 I g CH CH cu C N=N CH -CCH 1\ B/ 0: N O N-(CHflz-N-CH;

N N/ H: i

11B: N NH, A and CHI-010 s c 1 rs-rmm: C N=N- |3Hfi CH 101. The quaternary dyes of Belg. Pat. No. 609,667,

\ O=C N a N (E 0 NE:

0H5 i 9 94. The quaternary derivatives of the dyes of U.S -CH,CH:N( a)a Pat. No. 3,099,653 as 0 g 63 Y H S\ HO, NHCH:CHaCHzN(CHa)t I J V V H I v V V u /CN=N' 102. The quaternary dyes of U.S. Pat. No. 2,737,517,

as N i O O NH:

95-97. The quaternary derivatives of the dyes of British Pat. No. 459,594, as

9 I N=N cmcin-o-cmcm mcimn CHI 103. The quaternary dyes of British Pat. No. OCH H V g e I-=N OCH;CH:N(CH:)1

CzHs

The preceding list of dyes should not be construed as being restrictive. The list is intended to exemplify the wide variety of chromophores appiicable in this invention, e.g., monoazo, disazo, heterocyclic diazo or coupler, anthraquinone, quinophthalone, diphenylamine, etc. indeed, it is believed that all of the dyes disclosed in the foregoing references having localized, pendant positive charges will form stable, water-insoluble pastes as described subsequently, and all such disclosure of the foregoing references are incorporated herein. The alkylene group serves as an insulator since it is bonded to neighboring atoms through sigma bonds and does not possess pi electrons, nor an unshared electron pair, available for delocalization, i.e., resonance, with the positive charge.

2. The Anion Arso? The cationic dyes discussed in Part B( 1) immediately above are most commonly taught in the patent literature as possessing adequate water solubility. Water solubility is achieved by preparing the dye as salts with anions usually selected from the following list: Cl Br mp? SO zncl, cH,so,, C H SO CH -O-SO 6 C H O-SO C hi -SO 6 CH C H,,SO 6 (ortho or para), HCOO 6, CH COO C H COO ,C H,COO 'c1 cu, coo ,c,H, .coo the lactate, oxalate, tartrate or citrate ion. When produced with these ions, the dyestuffs are sufficiently soluble in water to be applicable to polyacrylonitrile fibers from aqueous solution.

in the present invention, selected substituted carbocyclic aryl sulfonates, ArSO are employed in place of the water-solublizing anions disclosed above. These selected arylsulfonates provide tight salts with the cationic dye which are water-insoluble at room temperture, may be dispersed with selected anionic dispersing agents, are compatible (i.e., do not co-precipitate by ion exchange) with acid dyes, anionic thickeners, and like ingredients of pad baths, and which fulfill the objectives of this invention as stated previously. in particular, they may be applie applied a continuous Thermosol technique to acid-modified polyacrylonitrile and polyesters.

The substituents permissible on the carbocyclic arylsulfonate may vary widely. It has been found that permissible substituents on the aryl sulfonates are those whose combined effect increases the acidity of the corresponding benzoic acids to a certain degree. More specifically, it has been found that any substituents which increase the acidity of benzoic acids, in an aqueous medium, by at least 0.6 of a pKa unit, when added together, are useful substituents for the carbocyclic aromatic sulfonic acids used as complexing anions for the localized pendant charged cations in this invention. Thus, on pages 592-593 of the Determination of Organic Structures by Physical Methods, Vol. I, by Braude and Nachod, published by Academic Press, Inc., New York, 1955, is a table listing pKa increments for various substituents. Any of the listed substituents may be employed so long as their pKa sum has a value of 0.6 or less. Thus, as readily seen from inspecting pages 592-593, this requirement is readily fulfilled by three preferred complexing agents, as follows:

Hi0 NO:

N01 NO:

ApKa 0.75 ApKa l.04 ApKa 2.79

in addition, the following monosubstituted benzenesulfonic acids may be employed as complexing anions useful in attaining the objectives of this invention The list for operable polysubstituted carbocyclic aromatic sulfonates becomes much larger since the effects appear to be additive, as previously illustrated with two of the three preferred complexing agents. For example, the following complexing anions may be specifically mentioned as applicable:

ApKa 3-methylsulfonyl-5-chlorobenzenesulfonate 0.93 3-trifluoromethyl-6-ethylbenzenesulfonate 0.84

3,5-dicarboethoxybcnzenesulfonate 2,4-, 2,5 3,5-dichlorobenzenesulfonate 2-methoxy-4-methylsulfonylbenzenesulfonate These polysubstituted benzenesulfonic acids, useful in this invention, are also suggested by the data on pgs. 594-594 of the Braude reference. On these two pages, pKa values, are listed as compared to the reference, benzoic acid itself. Since a lower pKa than benzoic acid, 4.20,'indicates a stronger acid than benzoic, a simple subtraction of the listed values from 4.20 gives the ApKa. Thus, based on pages 594-595, the following benzene-sulfonates are also applicable in this invention. Many of these pKa values are somewhat surprising based on the values given for the monosubstituted benzoic acids shown on page 592-593. These apparent anomalies are usually rationalized on the basis of steric effects, as well as their electrical, i.e., inductive and resonance effects.

ApKa 2,fi-dimethylbenzenesulfonate 0.99 2,4-dibromobenzenesulfonate l .50 2,5 -dinitrobezcnenesulfonate 2.58 3,4-dinitrobenzenesulfonate l .38 4-nitro-B-methylbenzenesulfonate 0.69 2,4,o-trimethylbenzenesulfonate 0.77 2-nitro-4,5-dimethoxybenzenesulfonate -l .7i 2,3-dinitro-5,6-dimethoxybenzenesulfonate .2.84

Additional substituted compounds are effective in this invention. Several are listed below with reference to their Hammett sigma constants. The pKa limitation is not being changed here since the Hammett sigma constants can be derived from the degree of dissociation, i.e., ionization or pKa of substituted benzoic acids in an aqueous medium. A convenient list of Hammett sigma constants is available on p. 87 in Physical Organic Chemistry, 2nd Edition, by J. Hine, McGraw- Hill Book Co., Inc., 1962. Using Hammett sigma constants, the requirement is that sigma be equal to or greater than +0.6. This requirement is the equivalent of the requirement that the sum of the pKa's be equal to or less than 0.6. Thus, the following compounds may be cited:

Hammett sigma value 3,S-dicarbomethoxybenzenesulfonate +0.64 +0.74

3-sulfonamido-4-p-nitrophenylbenzenesulfonate +0.72

Finally, several compounds are readily applicable as anions in this invention, for which ionization data is not conveniently found in the literature. Thus, in changing from benzene to naphthalene sulfonates, more than just the ionization constant must be considered to describe the effect on the solubility of the cationic dye salts. For example, although the pKa values of benzoic acid and fi-naphthoic acid are similar (3.20 and 3.16, respectively), the latter is 30 times less soluble. Since B-naphthoic acid is more insoluble than benzoic acid, it is clear that any substituents on the B-napthoic acid whose pKa sum is equal to or less than 0.6 will be operable in this invention. Some such compounds include the following commercially available carbocyclic aromatic sulfonates:

-, and 8-acetamido-Z-naphthalenesulfonate 1-, and Z-anthraquinonesulfonate 2-chloro-3 ,5-dinitrobenzenesulfonate 2-chloro-5-nitrobenzenesulfonate 4-chloro-3-nitrobenzenesulfonate 8-cyanol -naphthalenesulfonate l-, and 2-naphthalenesulfonate 5-,, and 8-nitro-l-naphthalenesulfonate 5, and 8-nitro-2-naphthalenesulfonate 2,6-dimethy'l-8-, and -3-naphthalenesulfonate Acenaphthene-S-sulfonate C. THE ANIONIC DlSPERSlNG AGENTS The dyes of Part A( l) and the carbocyclic aromatic sulfonates of Part A(2), and the dyes of Part B( l) and the sulfonates of Part 8(2) are each combined to yield water-insoluble salts. The ion air formed between the cationic dyes and the ArSOor ArSO? complexing agent is a very tight, i.e., very slightly dissociated, ionpair. Thus, it is possible to prepare stable, highconcentrated dispersions of these ion-pair salts dispersed with an anionic dispersant.

The choice of the anionic dispersant is important. A dispersant is needed which is relatively non-foaming and will not stai'n any fibers in a blend to bedlyed. The dispersant should be one which is useful i.e., compatible, with a very wide range of dyes of widely varying type. in particular, the dispersant, since it is anionic, must not compete excessively with the carbocyclic aromatic sulfonate originally present in the ion-pair salt, since severe competition, i.e., ion exchange, would destroy or seriously limit the dispersion stability. in addition, since the cationic dye-arylsulfonate salts are water-insoluble, they mustbe finely dispersed to provide stable products for the dye industry. Furthermore, due to the desirability of lower-cost dyes, the use of economical dispersing agents, in the pastes of this invention, is preferred.

Dispersants which satisfy all these requirements are the lignin sulfonates and salts of suifonated naphthalene-formaldehyde condensates. These dispersing agents are well known and are well suited for use in this invention. They are particularly adaptable for use in this invention because the salts are sufficiently insoluble to be compatible with the lignin sulfonate and sulfonated napthalene-formaldehyde condensate, and the salts have a sufficiently high melting point to permit milling is further agitated approximately and to provide stability at 40 to 50C. (usual storage or heated pad bath temperature). Salt-forming arylsulfonates containing greater than about eight aliphatic carbon atoms are not particularly useful in producing the water-insoluble salts. Some common trade names linked to readily available commercial lignin sulfonates are as follows:

Polyfon sodium salt of sulfonated lignin (West Virginia Pulp and Paper Co.)

Reax sodium salts of sulfonated lignin derivatives- (West Virginia Pulp and Paper Co.) Marasperse partially desulfonated sodium lignosulfonate (American-Can Company) Polyfon 0 (which contains i mole sulfonation per lignin unit of 840 gms.), chiefly because of its low cost and utility, is a preferred dispersing agent.

Some common trade names of readily available sulfonated naphthalene-formaldehyde condensates are as follows: Blancol (sodium salt) and Blancol N (sodium salt) General Aniline and Film Corp.; and Daxad llKLS (polymerized potassium salt of alkyl naphthalene sulfonic acid);

No. 15 (polymerized sodium salt of alkyl naphthalene-sulfonic acid);

No. 17 (polymerized sodium salt ofalkyl naphthalene-sulfonic acid in non-dusting granular form).

D. PREPARATION OF THE SALTS The preparation of the cationic dye-arylsulfonate salts of this invention is carried out by initially preparing an aqueous solution of slurry of the cationic dye associated with its customary, water-solubilizing anions. The slurry or solution is most conveniently prepared by using from 2-8 times as much deionized water by weight, as pure dye, at a temperature of from 2070C., accompanied by stirring for 1-2 hours until solution is complete, or the slurry is uniform.

The cationic dye is then precipitated as the water- .insoluble cationic dye-arylsulfonate by adding a slight excess of a molar equivalent of the appropriate selected arylsulfonate, usually as its sodium salt or free acid, over an approximate one-half-3 hour period to the aqueous slurry or solution maintained at approximately 2070C. Upon completion of the addition, the slurry 1-3 hours at 20-70C., to insure complete precipitation, then cooled to room temperature and filtered.

The filter cake is washed with fairly large amounts of deionized water since it is necessary to essentially completely remove the residual inorganic salts. Since many water-soluble cationic dyes are customarily added as their chloridesalts, completion of washing is readily indicated by obtaining an essentially chloride-free wash filtrate. in the event that other inorganic anions were originally associated with the cationic dye, comparable, well-known, simple tests may be substituted for the well-known test for chloride anion. In this manner, yields greater than can be obtained, frequently greater than The elemental analyses available indicate that the stoichiometry of the cationic dyearylsulfonate salt is as would be expected to balance the electrical charges, i.e., 1:1.

The pH, during the preparation of the aqueous solution or slurry of most of the water-soluble dyes and the slurry of the water-insoluble arylsulfonate salts, is not critical. The pH may vary from approximately 2-10. The preparation of aryl-sulfonate salts of triarylmethane cationic dyes requires a fairly strong acidic medium, e.g., a pH of about 2-4. That is, in alkaline media, a triarylmethyl carbonium ion would be converted to the unreactive (for salt formation) carbinol derivative. lndeed, whatever the pH during the preparation steps, the washing step with deionized water to eliminate inorganic salts will also nearly completely wash out any excess acidity or alkalinity such that the pH of the resulting wet filter cake is essentially neutral. Since the subsequent milling or dispersing step is accomplished at a pH of approximately 79, the washing out of excess acidity is most beneficial.

E. PREPARATION OF THE AQUEOUS DISPER- SlONS OF THE SALTS AND THE ANlONlC DIS- PERSING AGENTS ln preparing the pastes or dispersions of this invention, the usually wet press cake of the cationic dyearylsulfonate salts is milled with the anionic dispersing agent and sand in the conventional manner. Thus, the press cake is charged into the milling (grinding) apparatus along with dispersant and sand. The dispersant, a lignin sulfonate or sulfonated naphthaleneformaldchyde condensate, is added in proportions varying from approximately 10-200% (by weight) based on the weight of dry, pure cationic dyearylsulfonate salt. The weight of sand used, based by weight on pure, dry, cationic dye-arylsulfonate salt may vary from approximately 300 to 700%. The water requirements cannot be easily defined except to say they must be adequate to provide a paste of sufficient, but not excessive, fluidity to permit the shearing'action of the mill to reduce the particle size to the desired level.

The aqueous suspension is ground (milled) in a sand or colloid mill until the particle size is preferably reduced to approximately 1 micron. The temperature of the mass is usually maintained from approximately 2070C. The pH of the dispersion is approximately 8-9. The time usually required to prepare the dispersion with preferable particle size is approximately 2-5 hours. Such a short time is adequate since the cationic dye-sulfonate salts of this invention are readily dispersed. Upon attaining the desired particle size, which may be as large as -50 microns, the aqueous dispersion of dye salts is filtered to separate it from the sand. The dispersions of this invention are obtained as the filtrate, leaving the sand as the filter cake, in which the dispersant is present in amounts of 125% based on the weight of solids. Very efficient recovery of the dye salt charged is obtained.

Several additional, optional steps take place between obtaining the filtrate and actually employing it in dye applications. Thus, it is customary to standardize the dispersion to obtain a reproducible, reliable strength relationship between various dye batches. This standardization is frequently arbitrary, usually dependent upon the tinctorial strength of the cationic dye chromophore. With the cationic dye-arylsulfonate salts of this invention, the standardized pastes contain from 5-40%-by-weight pure, dry dye salt.

In the process of standardizing the inventive dye-salt pastes, dextrin, sodium carboxy methyl cellulose, humectants, anti-foam agents, bacteriocides, fungicides,

and additional anionic dispersant are frequently added.

Typical humectants are glycerol and sorbitol. Various commercial preparations are available for reducing foaming tendencies, as Nalco" 71-D5, a liquid formula containing polyglycol and fatty acid types of sur- 1 face active agents, etc. Bacteriocides and fungicides are illustrated by paraformaldehyde, sodium silicofluoride, and commercial preparations such as the sodium salt of pentachlorophenol.

The resulting, standardized aqueous dispersions are stable for at least six months and many are stable for over one year. This outstanding prolonged stability in high concentrations is one of the surprising advantages of this invention over the prior art.

E PROCESS IPYEING The cationic salt components of the dispersions of this invention can be applied to anionic fibers and their blends by several different dyeing methods. A detailed description of each method is included below. To summarize, the dispersed salts can be applied by the Thermosol method sa described in Gibson US. Pat. No. 2,663,612. The dispersed cationic salts can be applied by pad-roll to polyethylene terephthalate and acrylic fibers or blends of such fibers with cotton, achieving compatibility with'anionic dyes in the latter case; by pad steam and printing, and by the exhaust method.

The anionic polymeric substrates, for which the inventive dye-sulfonate salt dispersions have particular utility, include shaped articles such as acid-modified acrylic fiber having acid sites, for instance the sulfonate-modified acrylic fibers described in US Pat. Nos. 2,837,500, 2,837,501, and 3,173,747; also acidmodified polyester fiber such as polyethylene terephthalate fiber containing metal-sulfonate groups as described in US. Pat. No. 3,018,272, the polymerdisclosing portions of which are incorporated herein by reference.

In addition to the acrylic and polyester fibers noted above, other types of fibers are advantageously colored by the dye compositions of the present invention. These include the trade name fibers listed as described in the reference J.Soc. Dyes & Col., 77, No. 12, page 618 (December, 1961).

A wide variety of non-basic dyeable polyester, acrylic, polyamide, and cellulosic fibers may be coemployed since the cationic dye-arylsulfonate salts are designed mainly for the acid-modified acrylic or polyester fiber. 7

A description of the various dyeing processes in which the compositions of this invention may be employed as follows:

l. Thermosol Method This method is particularly applicable to fibers known as *Orlon-42', Dacron-64, and to blends such as Orlon"-42/ viscose rayon, Acrilanllcellulose acetate/rayon, Orlon-42/ nylon/cotton and Dacron- -64/Dacron-54/cotton. The Thermosol method is, in general well known and offers the advantage of a continuous process which requires only a short contact period. The general process is described in US. Pat. No. 2,663,612.

The Thermosol process is particularly applicable to blended fabrics, particularly those containing cellulosic fibers, since during the padding operation, the cationic dye-arylsulfonate salt will be padded on both fibers, i.e., cellulosic and acid-modified synthetic. Since cationic dyes have no affinity for cellulosic fibers, a large amount of dye would be wasted unless considerable transfer of cationic dye-arylsulfonate salt occurred from cellulosic to synthetic. Surprisingly, very good transfer is observed with the compositions of this invention on blended fabrics; indeed, cotton or cellulosic fibers are only slightiy stained by the cationic dyearylsulfonate paste following Thermosol treatment. This characteristic of minimum stain on the cellulosic component is necessary since any residual cationic dye on the cellulosic would yield a fabric with poor lightfastness and poor washfastness.

Moreover, in actual dyeing of blends, the pad bath will usually also contain the vat, fiber-reactive or direct dyes for conventional dyeing of the cellulosic, following Thermosol dyeing continuous fixation of the cationic dye on the acid-rnodified fiber. That is, following fixation of the cationic dye, the vat dye would be reduced'with caustic-hydrosulfite to enable the leuco-vat dye to penetrate the cellulosic fiber. This reducing agent is also a very effective stripping agent of the slight residual cationic dye-arylsulfonate paste on the cellulosic fiber that has not completely transferred to the acid-modified synthetic fiber. This dual role of a conventional procedure for dyeing cellulosic fibers makes the previously mentioned fiber blends preferred.

A more detailed description of a typical actual dyeing procedure in conjunction with vat dyes is as follows: A pad bath solution (10 g./l. dye strength) is prepared by stirring the dispersed cationic salt paste (2 g., 200:1.00 vs. the conventional cationic powder) into a mixture of 20% Superclear Gum (10 ml.) (a refined solution of natural gums sold by Jacques Wolf and Co.) and l% Merpol SH (4 ml.) (a nonionic ethylene oxide condensate with a fatty alcohol), then diluting with water to 100 ml. The pH is adjusted to 6.5 to 7.0 by adding either tetrasodium pyrophosphate or monosodium phosphate. The fabric is saturated with the pad bath solution and then squeezed to remove the excess (pick up 65%). The pad is air dried at 120F. and then heated in a Thermosol oven at 400 to 430F. for 90 sec. to fix the dye in the fiber. The Thermosoled pad is then saturated with a solution containing sodium hydroxide (75 g.ll.) and sodium hydrosulfite (75 g./l.), then steamed at 2l5-225F. for 1 minute. Any vat dye present is re duced at this point. in addition any of the cationic salt which did not fix in the preceding step is scoured off. After rinsing the pad in cold water, it is then treated at 120F. for minutes in a sodium perborate solution (2.5 g./l.) to oxidize the vat dye. After a rinse in cold then hot water, the pad is soaked for -5 min. at about 210F. in soap solution (0.2% sodium oleate). After another rinse in cold then hot water, the pad is dried. If a vat dye is not co-applied with the invention pastes on Orlon/cellulosic blends, the caustic-hydro scour would still be necessary to remove trace stains on the cellulosic fiber; however, the perborate treatment would not be employed.

This commercially valuable, continuous process is possible only since the compositions of this invention can be applied by fast, thermal (Thermosol) techniques, and since the inventive pastes are compatible,

in high concentrations, with other pad-bath adjuvants. I

The strength and/or shade of the salts when applied by the Thermosol method is much improved over the strength and/or shade of the corresponding conventional powder or heteropoly acid pastes. On 100% Orlon-42 fiber, the percent fixation and build-up with increasing dye concentration varies with the anion used. it is possible to achieve nearly quantitative fixation values (95l00%) on l00% acid-modified Orlon with selected arylsulfonates.

For fabrics made from intimate blends of polyfibers (polyamides, acrylics, polyesters) with cellulosic (cotton, rayon) fibers, an important styling method is twotone or cross-dye coloration wherein the component fibers are dyed to contrasting colors or to widely differing shades of the same color. Because of the considerably lower abrasion resistance of the cellulosic fibers compared to the polyfibers, the wearing of garments made from the cross-dyed fabrics induces unsightly color changes (commonly termed frosting) at the points of most severe abrasion. The color change is always toward the color of the polyfiber component. While the problem has been always troublesome, the situation has become completely intolerable with the advent of durable press. This, by virtue of the high degree of crosslinking induced in the cellulosic fiber,

drastically reduces its already low abrasion resistance.

A route toward greatly minimizing the frosting problem is the use of a three-component blend of about one-third cellulosic and one-third each of two different polyfibers, each of which is dyeable in many cases, with a specific class of dyes having little substantivity for the other. When'disperse dyes are used for one component in a triblend fabric, e.g., for unmodified polyester fiber, cellulose acetate, etc., it must be recognized that disperse dyes are also substantive to nearly all synthetic fibers, whether acid-modified or not. Hence, the acidmodified synthetic fiber is usually dyed to a deep shade with the pastes used in this invention, and the other to a considerably lighter shade. The cellulosic component is dyed to antermediate shade and hue. in use, when the preferential abrasive loss of the cotton occurs at points of severe wear, the combined shade of the two polyfibers tends to mask any color change induced thereby.

The validity of the triblend approach has been demonstrated with the following three combinations of tihers:

I. Polyamide (acid dyes), acid-modified acrylic (cationic dyes), and cotton (direct, vat or fiberreactive dyes);

2. Basic-modified acrylic (acid dyes), acid-modified acrylic (cationic dyes), and rayon (direct, vat or fiber-reactive dyes);

3.'Acid-modified polyester (cationic dyes), standard polyester (disperse dyes), and cotton or rayon (direct, vat or fiber-reactive dyes).

4. Acid-modified acrylic (cationic dyes), cellulose acetate (disperse dyes), and rayon (direct, vat or fiber-reactive dyes).

Because it has not previously been possible to apply cationic dyes satisfactorily by the Thermosol process, the dyeing procedure for the triblend fabrics has been discontinuous; i.e., while the dyeing of two of the fibers could be carried out on a continuous basis, it was necessary to interrupt the process to apply the cationic dyes by a piece dyeing procedure, as in a beck or jig. This requirement has so increased the finished fabric costs that the triblend concept has had only limited commercial adoption. However, the dye compositions of this invention, by virtue of their applicability by the Thermosol process, now permit the coloration of each component of the triblend by an integrated continuous process, thusnegating the previous cost disadvantages and consequently permitting the application of the triblend concept to a much broader range of fabric styles and fabric costs.

2. Pad Steam Pad steam is also a continuous method. One requirement for this method is compatibility with acid and direct dyes which the dye compositions of this invention can accomplish. Another requirement, more difficult to meet, is to achieve full shade and strength dyeings after 30 sec., preferably, or in no longer a time than 2 minutes at about 110C.

There are two particular advantages which the pad steam technique has over Thermosol pertinent to this application. One, the padded fabric is not dried. As a consequence, during the dyeing of an acid-modified acrylic or polyester blend, it is possible for the dye to transfer via solution from the blended fiber to the anionic fibers. Two, this dyeing method represents a useful continuous method for dyeing Orlon-42/ wool blends. Wool cannot be subjected to Thermosol temperatures for it will char. Other fibers and fiber blends adaptable for use by the Pad Steam procedure include Dacron"-64/ wool, Orlon-42/ and Dacron- 64/Dacron"-54/cotton.

A typical pad steam procedure is as follows:

A pad bath solution g./l. dye strength) is prepared by stirring the dispersed cationic salt paste (2 g., 200:100 vs. the conventional cationic powder) into a mixture of 20% Super-clear Gum (7.5 ml.), a refined solution of natural gums sold by Jacque Wolf 8:. Co, and 0.1 g. of an alkyl benezene sodium sulfonate, a wetting agent, then diluted with water to 100 ml. The pH is adjusted to 6.5.

The fabric is saturated with the pad bath solution and then squeezed to remove the excess (pick up 65%). The pad is then steamed at 100C. for 5 min. after which it is scoured in a soap solution at 140F. for min. The pad is rinsed in cold then hot water and dried.

1f the fabric is a blend containing wool, it is desirable to first wet it out in a l g./l/ solution of Alkanol WXN (a modified sodium alkylaryl sulfonate) at 180F. then squeeze to remove any excess.

3. Pad Roll The pad roll operation is a semi-continuous method.

In this process the fiber is saturated with the pad liquor,

squeezed to remove any excess, then rolled and steamed at 100C. for several hours. Since considerable expense is saved if both fibers can be dyed in one operation, compatibility is very desirable. Heteropoly acid complexes are not satisfactory because they do not build-up well and produce a heavy stain on cotton; however, the compositions of this invention are satisfactory for the pad roll method.

The general procedure used is as follows:

A pad bath containing 40 g./l. of the dispersed cationic dye-aryl sulfonate salt (IO-20% A.1.) and4 g./l. of a wetting agent, such as Merpol SH (a nonionic ethylene oxide condensate with a fatty alcohol), is prepared with the pH adjusted to 6.5. The fabric is saturated with pad bath and squeezed to remove any excess liquor (pick up 60%). The wet pad is rolled and heated at 100C. for 4 hours to fix the dye in the anionic fiber. Unfixed dye and other chemicals are removed by a scour in 10% caustic-hydro-solution at 120F.

The pad is rinsed in clear water and dried.

Fibers adaptable to this process include Orlon-42 and Orlon-42/cotton.

4. Exhaust Dyeing It has been possible to dye both fibers of an acidmodified acrylic or polyester blend in one bath by making a careful selection of the dyes used, as well as the temperature of bath at the time of their addition. At higher bath temperatures, above about 160F., many of the insoluble salts formed by anionic and cationic dyes are completely dissociated. Surprisingly, the cationic complexes of this invention provide complete compatibility with anionic dyes even at room temperature by the exhaust dyeing procedure, which greatly simplifies the dyeing operation. The general procedure used is as follows:

Dyeings are made using a volume of solution approximately 40 times the weight of the fiber. For a 1% dyeing on skeins, the dispersed cationic salt (2002100 versus the standard Powder) is added at 2%. the weight of the fiber. The dye bath is prepared by stirring the dye salt into a solution containing 0.5% Alkanol HCS, 10% sodium sulfate, about 1% glacial acetic acid (pH 4.5), and 2% Retarder LAN. The dye bath is held at the boil for approximately 1% hours. The dyed fabric is then rinsed in cold followed by hot water and dried.

Fibers adaptable to this procedure include Orlon- 42, Orlon-42/cellulosic fibers, Orlon- 42/nylon/cotton and Dacron"-64/Dacron- 54/cotton. 5. Printing The dispersed cationic dye-arylsulfonate salt (5 pts. containing 10 to 20% A.I.) and citric acid (2 pts.) are mixed into a 3% solution of locust bean gum in water pts.). Other adjuvant may be added (e.g. ZnSCN as an auxiliary for application to triacetate fibers), since the inventive pastes are compatible with the ones commonly employed.

When the printing paste is uniform, it is applied to the fabric and then dried in a hot air oven or over heated drums at l60.-300F. The dye is fixed to the fibers either by steaming the fabric at 2 l 2-250F. for 20 to 60 minutes or by Thermosol development at 400430F. for 60 to seconds.

Dyes which have not been fixed to the fabric and other chemicals are removed in a detergent scour (0.5% solution of a sodium alkyl sulfate) at F. The fabric is rinsed in clear water and dried.

Q-MIBEE L QS- Examples l-XXl, which follow, are directed to the preparation and use of dye salts having the formula D L619 AR'SO Description of a dye by-number, e.g., Dye 18, in the examples, refers to the dye numbered 18 in the specification.

EXAMPLE 1 Preparation of Salt The carbin'ol derivative of Dye 18 (100 g., 0.24 mole) was 'slurried in 600 ml. of deionized water at 20-25C. When uniform, 4-nitrotbluene-Z-sulfonic acid (65.5 g., 0.3 mole) was slowly added in 5 g. portions over a period of 2 7% hours. The resulting slurry was held at 2025C. For 3 hours. The pH of the slurry at this point was about 1.0. The precipitate was filtered and washed with 500 to 1000 ml. of deionized water; the pH of the filtrate at the end of the wash was about 2.5. The precipitate was partially dried by suction.

Weight of the wet cake 300 g.

solids 40% calculated dry wt. 120 g. 81.1% of theory M.P. l42-145C. Dispersion The above wet cake was milled with 25 g. Polyfon" O and 750 g. of fine sand. After about 3 hours at 2030C. the particle size was reduced to 1 or less. The sand was filtered off.

Weight of the paste 636 g. Estimated recovery based upon the amount of carbinol originally charged 78% (by spectral measurements). Standardization Dowicide G (sodium pentachlorophenate) (l g.) and sodium silicofluoride (l g.) slurriedin H ml.) was dropped into the above paste with agitation. 70% sorbitol (100 g.) was added, and the paste stirred for minutes, then filtered through milk paper to remove large particles.

Spectral strength 200:100 vs. alternatively standardized powder )tmax 618 mu, a 21.0/g. in 80% Dimethylacetamide/% H O EXAMPLE ll The same procedure'was used as described above in Example 1 with the following exceptions: Preparation of Salt Crude Dye 13(200 g., 182.6 g. 100%, 0.41 mole) was slurried in deionized water (600 ml.), and 4-nitrotoluene-2-sulfonic acid (91.4 g., 0.42 mole) was slowly added. The product when filtered off was washed with 2 liters of deionized water.

Weight of the wet cake 554 g.

solids 37% 1 I Calculated dry weight 205 g. 89% of theory M.P. liquefies at l08l09C.; solidifies on further heating; M.P.= 207-208C. Amax 526.5 mg; a l26.l/g. in 50% aqueous ethanol Dispersion Part of the above wet cake (430 g. 159 g. dry wt.) was milled with "Polyfon 0(15 g.) and fine sand (750 g.) at 2030C. After milling about 3 hours, the particle size was reduced to l p. or less. The sand was filtered and washed with 150 g. of 10% Polyfon 0 solu- -tion.

Weight of the dispersed paste 574 g.

Spectral strength 801100 vs. corresponding powder Standardization The above paste was stirred and "Polyfon0(25 g.)

was added in deionized water (600 ml.) as was 70% EXAMPLE lll Preparation of the Naphthalene-2-Sulfonate Salt of Dye l8 s 0 ,9 e -NH: O i

REEL.

Dry yield based on solids 30.8 g. (81% of Theory). MP. 263265C. r i e...

The above cake (5.0 g. dry weight) was milled with Blancol (1.0 g.) and fine sand (25 g.) at 50-55C. until the particle size was uniform and about 1,4 or less (4 to 6 hrs.). The dispersion was diluted with water to reduce the viscosity and the sand filtered off and rinsed with deionized water (7 ml.).

Wt. of the recovered paste 28.5 g. (about 10% Al.)

When applied to Orlon-42 and Orion blends by the Thermosol method, speck-free uniform pads are obtained similar in shade to aqueous dyeings of the corresponding dye 18 powder.

EXAMPLE IV CH: CH:

OCH; C

@ocm ms Crude dye 4 (140 g.; 0.38 mole was slurried in deionized water (2500 ml.) at room temperature, and when uniform, a wet cake of 4-nitrotoluene-2-sulfonic acid (133 g.; 67.3% 0.46 mole) was slowly added over a period of 6 hours. The mixture was stirred 16 hours at room temperature. The product was filtered and washed with deionized water until the pH of the filtrate was 4.9 and isolated as a wet cake.

Dry yield based on solids 177 g. of Theory). M1. 199.S-200C.

Dispersion Fine sand (88.5 g.), Polyfon" 0 (15 g.) and sufficient water to provide fluidity were slurried in a sand mill at room temperature and the above wet cake, containing the crude dye4 complex (177 g. dry weight) was slowly added mixed with Polyfon 0 (5 g.) over a period of 4 hours. The mixture was milled at 40-50C. for l hour during which time additional Polyfon" 0 (10 g.) was added. The particle size was uniform and about lp. or less. After diluting with deionized water (250 ml.) to reduce the viscosity, the sandwas filtered off and washed with 10% aqueous Polyfon" 0 solution (50 ml.). The filtrate was slurried with dextrin (30 g.), sodium silicofluoride (3 g.) and Dowicide G g)- Wt. of paste 704 g. Dyeing When applied to Orlon-42/wool or Dacron- 64/wool blends by the pad steam method, speck-free uniform dyeings are obtained similar in shade to aqueous dyeings of standardized dye 4 powder.

EXAMPLE IV Preparation of the Salt of Dye 4 and Sodium-m- Nitrobenzene-sulfonate Crude dye 4 (80 g., 0.2 mole) was slurried in 500 ml. of water at 5060C. After about 1 hour when the slurry was uniform, sodium-m-nitrobenzene sulfonate (45 g., 0.2 mole) was slowly added over a period of one-half hour. The mixture was held 3 hours at 50-60C., then cooled to room temperature, filtered, washed free of C1 with water (250 ml.) and sucked down.

Two runs carried out in the manner gave a total wet cake weight 572 gms. solids 41% Calculated dry weight 235 gms.; 99"% of theory based on spectra. )tmax 416mp.; a 87.7/g. in 50% aq. ethanol M.P. 144146C. Dispersion The above wet cake was milled with Polyfon (45.

gms.) and fine sand (875 gms.). it was necessary to evaporate off some of the water by allowing the temperature to rise to 60C. After about 2 hours, the particle size was reduced to 1;]. or less. Polyfon 0 g.) was added, and the milling continued one-half hour longer and then filtered through milk paper. The sand was washed with a little deionized water, adding the wash to the filtrate.

Weight of the paste 684 gm.

Spectral strength 120:100 vs. standardized dye 4 powder Calculated recovery of dye based upon the amount of crude orginally charged 99%. Standardization Dowicide G*(1 g.) dissolved in water (10 ml.) and sodium silicofluroide (1 g.) slurried in water (10 ml.) were slowly dropped into the above paste with agitation. 70% sorbitol (140 g.) and water (35 ml.) were added, and the paste stirred for minutes, then filtered through milk paper to remove large particles.

Strength 2002100 vs. standardized dye 4 powder. A 415mg; a 15.9/g. in 50% aq. ethanol EXAMPLE V Preparation of the Dimethylisophthalate-S-Sulfonate Salt of Dye C.l.42,000

OOCH:

A wet cake of the carbinol of the dye represented by C.I. 42,000 (69.3%; 16.0 g.; 0.03 mole was slurried in deionized water (80 ml.) at room temperature, and when uniform, HCl was added to bring the pH to about 1.0, thus converting the carbinol to the bright green carbonium ion. Di-methylisophthalate-S-sulfonic acid (9.0 g.; 0.033 mole) was added over a period of 2 hours. The product precipitated and was filtered off, washed with deionized water and air dried.

Yield 20.8 g. (not completely dry) Dispersion The above product (10 g.) was slurried with sufficient'deionized water to provide fluidity in a sand mill. Polyfon 0 (1.0 g.) was added and when uniform, fine sand (40 g.). The mixture was milled at room temperature until the dispersion was uniform and the particle size about lp Additional Polyfon" 0 (2.0 g.) was needed during the milling. The paste was diluted with deionized water to reduce the viscosity,the sand filtered off and rinsed with deionized water (10 ml.).

.Weight of paste 44 g. (about 15% A.l.) Dyeing When applied by the Thermosol method to Orion- 42 blends, speck-free uniform dyeings are obtained with good strength and build-up. The shade is similar to aqueous dyeings of a standardized, powder-form of C.I. 42,000.

EXAMPLE vi 5 Preparation of the Salt of Dye l3 and 2,4-Dinitrobens lrfqaate oar-@sm Crude dye 13 (91%; 10 g.; 0.02 mole) was dissolved in deionize'dwater (300 m1 .)at 50-60C., and a solution of v2,4-dinitrobenz'ene sodium sulfonate (12.3 g.;

65%; 0.03 mole) in deionized water (200 ml.) was' slowly added. The product precipitated from solution. The mixture was cooled with agitation to room temperature, the precipitate filtered off and washed with cold deionized water. The salt was vacuum dried at Yield =1 1.8 g (97% of Theory) M.P. l-l88C.

Dispersion An' equivalent amount of product was milled as a wet 35 r r W W 36 EXAMPLE longer at room temperature. The precipitate was iso Preparation of the Salt of Dye 24 and 4-Nitrotoluene-2- lated by filtration and washed with cold water until the Sulfonate fi a fleie erlsss and dfteslefiw qkzd. ame

' ca. CH;

no cn=cnmcmcmorm -sme N65 N02 Crude dye 24 (20 g., 0.04 mole) was slurried in de- 1 The product was obtained as a high solid (76%) wet ionized water (200 m1.) at room temperature. -When cake. the slurry was uniform, 4-nitrotoluene-2-sulfonic acid Dry yield based on solids 14.55 g. (66% of Theory) (15 g.,0.07 mole) was slowly added over a period of 2 MP. 131-l33C. to 3 hours, followed by stirring 1 hour longer at room Dispersion temperature. The product was filtered off and washed A portion of the above wet cake (5.3 g. dry weight) acid free to Congo Red paper with cold deionized wawas slurried with Polyfon" 0 (0.5 g.) .in a sand mill at ter. The salt was isolated as a wet cake (8] g., 29.2% room temperature. When the slurry was uniform, fine lids), sand (35 g.) was added and the mixture milled at room Dry yield based on solids 23.7 g. (95% of Theory) temperature. After milling 6 hours, additional Polyp 182 5 184C I fon" 0 (0.5 g.) was added and milling continued 1 hour m -E 10- 7 y l longer. The particle size was uniform and about lp. or

Q less. The paste was diluted with deionized water to re- A Portion of the above Wet Cake y weight), duce the viscosity, the sand filtered off and rinsed with was slurried in a sand mill with Polyfon" 0 (0.5 g.). water (5 g). When the slurry was uniform, fine sand was added (25 Dyeing g.) and sufficient water to provide fluidity. The mixture The paste 20 about 15% AL) was mixed with was milled for about 2 hours at about 40-45C. The -bi (70%, 5 When applied by the Thermosol particle size was uniform at the end of this time and method to Da w 4 and s blends, about or l Additional Y O s form bright red dyeings with good fixation, build-up added and 15 longer- The Paste was diluted and fastness are obtained. The shade is similar to aque- I with deionized water to reduce the viscosity, the sand Gus dyeings f standardized dye 11 powden lt s?v imiilinss xitbsde izsyamr .t -t- "1 EXAMPLE ix The paste (16 g.; 15% Al.) was mixed with sorbitol Preparation of the Salt of Dye 23 and 4-Nitrotoluene-2- 7.0 2 a W s H v is .Svlfevae..-

sla Dyeing Crude dye 23 (20 g.; 0.05 mole) was slurried in de- When applied l0 and its blends y the ionized water (200 ml.) at room temperature. When Thefmqsol mfillhod, speck-free uniform dyeing e bthe slurry was uniform, 4-nitrotoluene-2-sulfonic acid tained. The shade is similar to aqueous dyeings of Dye (125 g ()6 l l l dd d over a i d f 24 standardized powder. 2 hours. After stirring 1 hour longer at room temperature, the product was isolated by filtration, and washed EXAMPLE vm acid-free to Congo Red paper with deionized water.

Preparation of the Salt of Dye l1 and 4-Nitrotoluene-2- The product was isolated as a wet k .ll'f2!@i Dry weight based on solids 18.8 g. (66% OfTheOI'y) CH, M.P.=207-209C.

0 (0,119! $6 2 5): Dispersion "-508 A portion of the above wet cake (3.8 g. dry weight) was slurried in ,a sand mill at room temperature with Polyfon" 0 (1.0 g.) When theslurry was uniform, fine COOCHs sand. (25 g.) was added and the mixture heated to 5055C. Additional Polyfon" 0 (1.0 g.) was added during the milling. When the particle size appeared unii form and about 1 1. or less, the milling was cooled to Crude y 1 I g, 80% Purity mole W88 Siufroom temperature. The sand was filtered off and rinsed ried in deionized water (200 ml.) at room temperature. ith 2% a ous Polyfon 0 solution (15 g.). 4-Nitrotoluene-2-sulfonic acid (1.0 g.) was added and D ein stirred 2 hours. Then more 4Nitrotoluene-2-sulfonic "T recovered filtrate and Wash, g-; acid 9.0 g., 0.046 mole total) was slowly added over a A1.) when applied by the Thermosol method to Da- .P 9d-9t ZJ QW Agitation was continued 1 h ronf. 64s. ..p59vi@1s.2s=5;frs sa f i xansui h lens-Sultan 37 good buildup and lightfastness. The shade is similar to aqueous dyeings of dye 23 standardized powder.

EXAMPLE x Preparation of the Salt of Dye 32 and 2,4-Dinitroben- Crude dye 32 (1.0 g.; 0.003 mole) was slurried in deionized water ml.) at room temperature. A solution of sodium 2,4-dinitrobenzene sulfonate (1.0 g.; 0.004 moles) in deionized water (10 ml.) was slowly added at 40C. A course precipitate formed.'The mixture was stirred at 3040C. for 45 min., followed by filtering off the product and washing with 100 ml. of deionized water. The product was isolated as a wet cake.

Dry yield based on solids 1.1 g. (70% of Theory) Melting point 227229Co a, 90.7; Amax 435 my. in 80:20 DMAC-l-l O Dispersion 7 A portion of the above wet cake (1.056 g. dry) was milled with Polyfon 0 (0.1 g.) and fine sand (5.0 g.) at 5055C. Additional Polyfon 0 (0.2 g.) was needed during the course of the milling to provide a uniform dispersion with a particle size of about 1 1.. The milling was cooled to room temperature and the sand filtered off. The sand was reslurried with 2% aqueous Polyfon 0 solution and dextrin (1.0 g.). When the slurry was uniform, the sand was filtered off. Both filtrates were collected and mixed.

Weight of paste 13.0 g. (about 57% A.l.) Dyeing When applied to 0rlon"-42 or its blends by the Thermosol method, speck-free uniform dyeings are obtained in heavy bright greenish yellow shades similar to aqueous dyeings of standardized dye 32 powder.

EXAMPLE Xl Preparation of the Salt of Dye 34 and 4- Nitroto1uene-2- sSulf nate.--

CHaCH:

, 3.8 ized water. The salt was isolated as a high solids (65%) wet cake.

Yield on a dry basis 6.27 g. (about 100% of They) The dry product =224227C.;

nd: mar Dispersion The above product was slurried as a set cake in a sand mill with sufficient water to provide fluidily. The pH was adjusted to 10.2 with concentrated NI-LOH (1 drop), Polyfon 0 (0.5 g.) added and when the slurry was uniform, fine sand (50.g.) added. The mixture was heated to 5055C. and milled for 4 hours. At the end of this time the particle size was uniform and about In. or less. The sand was filtered off and rinsed with deionized water (5-10 g.). Dyeing r The combined filtrate and wash containing the dispersed color (29 g.; 15% A.l.), when applied by the Thermosol method to Orlon-42- and its blends, provides speck-free uniform dyeings with outstanding lightfastness. The shade is'similar to aqueous dyeings of standardized dye 34 powder.

EXAMPLE X11 Preparation of the Salt of Dye 22 and 2.4-.

is reddish yellow; M.P.

438 my in 80:20 DMAC-H o.

Crude dye 22 (10 g., 0.03 mole) was slurried in deionized water ml.), and when uniform 2,4- dinitrobenzene sodium sulfonate (12,g.;0.04 mole) was slowly added, breaking any large lumps that formed. After stirring 1 hour longer at room temperature, the precipitate was filtered and washed with cold water. The product was isolated as a high solids (87%) wet cake.

Dry yield based on solids l 1.3 g. (61% of Theory) Melting Range 1 80C. (d) Dispersion Y The above product was milled as a wet paste (8.7 g. dry weight) with Polyfon" 0 (1.0 g.) and fine sand (25 g.) atroom temperature. To achieve a uniform dispersion with a'particle size of about 1 4., additional Polyfon" was needed (0.5 g.). The sand was removed by filtration.

Wt. of paste 35 g. (about 12% A.l.) The paste was slurried and Polyfon"0 (2.0 g.) and sorbitol (70%, 5

g.) mixed in.

Dyeing When applied to 0rlon"-42 and its'blends by the Thermosol method,'speck-free uniform dyeings are ob- Y tained similar in shade to aqueous dyeings of standardized Dye 22 powder.

Table I, immediately following, shows additional dispersions which may be prepared as generally described inthe foregoing examples: 

2. The composition of claim 1 wherein the water-insoluble salt has the formula D Ar''SO3 wherein D and Ar'' are defined as in claim
 1. 2. an anionic dispersing agent selected from lignin sulfonate or a salt of a sulfonated naphthalene-formaldehyde condensate; wherein D is a cationic base dye having a delocalized positive charge; K is a cationic dye having a localized pendant positive charge represented by the formula
 3. The composition of claim 2 wherein D is the cationic dye derived from a diphenylmethane, triarylmethane, xanthene, acridine, thiazole, indamine, azine, oxazine, thiazine or an azo dye having a delocalized positive charge.
 4. The composition of claim 3 wherein Ar'' is phenyl or naphthyl substituted with the substituents defined as in claim
 3. 5. The composition of claim 4 wherein Ar''SO3 is selected from 4-nitrotoluene-2-sulfonate, 2,4-dinitrobenzenesulfonate, naphthalene-2-sulfonate, dimethylisophthalate-5-sulfonate, o-chlorobenzenesulfonate, 3,4-dinitrobenzenesulfonate, 2,5-dinitrobenzenesulfonate, 2-nitrobenzenesulfonate, 3-ethoxy-carbonyl-4-cyanobenzenesulfonate, 3-trifluoromethyl-5-cyano-benzene sulfonate, 2,4-dibromobenzenesulfonate or 2,5-dichloro-benzenesulfonate.
 6. The composition of claim 1 wherein the water-insoluble salt has the formula K ArSO3 wherein K and Ar are defined as in claim
 1. 7. The composition of claim 6 wherein Z is an azo- or anthraquinone dye chromophore and Y is a covalent bond or alkylene of one to six carbon atoms.
 8. The composition of claim 6 Wherein Ar is phenyl or naphthyl substituted with the substituents defined as in claim
 6. 9. The composition of claim 8 wherein ArSO3 is selected from 3-nitrobenzenesulfonate, 4-nitrotoluene-2-sulfonate, 2,4-dinitrobenzenesulfonate, 3-methyltoluene-2-sulfonate, 2-nitro-4, 5-dimethoxybenzenesulfonate, naphthalene-2-sulfonate, dimethylisophthalate-5-sulfonate, 2-chlorobenzenesulfonate, 2-fluorobenzenesulfonate, 4-cyanobenzene sulfonate, or 2,4-di-chlorobenzenesulfonate.
 10. The aqueous dispersion of claim 1 wherein the water-insoluble salt has the formula
 11. The aqueous dispersion of claim 1 wherein the water-insoluble salt has the formula
 12. The aqueous dispersion of claim 1 wherein the water-insoluble salt has the formula 